U.S. patent number 10,487,291 [Application Number 16/111,418] was granted by the patent office on 2019-11-26 for detergent or cleaning agent having glda-enhanced antimicrobial effect.
This patent grant is currently assigned to Henkel AG & Co. KGaA. The grantee listed for this patent is Henkel AG & Co. KGaA. Invention is credited to Ulrich Baeumer, Roland Breves, Stefan Karsten, Christian Kastner, Birgit Veith, Mirko Weide.
![](/patent/grant/10487291/US10487291-20191126-C00001.png)
![](/patent/grant/10487291/US10487291-20191126-C00002.png)
![](/patent/grant/10487291/US10487291-20191126-D00001.png)
United States Patent |
10,487,291 |
Veith , et al. |
November 26, 2019 |
Detergent or cleaning agent having GLDA-enhanced antimicrobial
effect
Abstract
A detergent or cleaning agent that has an antimicrobial effect
and includes at least one tetracarboxylic acid or the salts thereof
in combination with at least one biocidal quaternary ammonium
compound.
Inventors: |
Veith; Birgit (Duesseldorf,
DE), Weide; Mirko (Duesseldorf, DE),
Kastner; Christian (Duesseldorf, DE), Baeumer;
Ulrich (Neuss, DE), Breves; Roland (Mettmann,
DE), Karsten; Stefan (Gummersbach, DE) |
Applicant: |
Name |
City |
State |
Country |
Type |
Henkel AG & Co. KGaA |
Duesseldorf |
N/A |
DE |
|
|
Assignee: |
Henkel AG & Co. KGaA
(DE)
|
Family
ID: |
58057159 |
Appl.
No.: |
16/111,418 |
Filed: |
August 24, 2018 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20190055493 A1 |
Feb 21, 2019 |
|
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
PCT/EP2017/053808 |
Feb 20, 2017 |
|
|
|
|
Foreign Application Priority Data
|
|
|
|
|
Feb 24, 2016 [DE] |
|
|
10 2016 202 846 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C11D
3/48 (20130101); C11D 3/2082 (20130101); C11D
1/62 (20130101) |
Current International
Class: |
C11D
1/86 (20060101); C11D 3/20 (20060101); C11D
1/62 (20060101); C11D 3/48 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
0000224 |
|
Jan 1979 |
|
EP |
|
9817759 |
|
Apr 1998 |
|
WO |
|
2004/009754 |
|
Jan 2004 |
|
WO |
|
2012055775 |
|
May 2012 |
|
WO |
|
2013064340 |
|
May 2013 |
|
WO |
|
Other References
PCT International Search Report PCT/EP2017/053808 Completed: Apr.
24, 2017; dated May 4, 2017 3 pages. cited by applicant.
|
Primary Examiner: Boyer; Charles I
Attorney, Agent or Firm: Krivulka; Thomas G.
Claims
What is claimed is:
1. A washing or cleaning agent comprising a) from 5 to 40 wt. % of
at least one anionic surfactant selected from the group consisting
of alkylbenzene sulfonate, alkyl sulfate and mixtures thereof, b)
from 0.5 to 25 wt. % of at least one non-ionic surfactant selected
from the group consisting of fatty alcohol polyglycol ether, alkyl
polyglucoside, fatty acid glucamide, and mixtures thereof, c) from
0.01 to 10 wt. % of one or more builders selected from the group
consisting of zeolite, polycarboxylate, sodium citrate, and
mixtures thereof, d) from 0.1 to 2 wt. % of enzymes selected from
the group consisting of proteases, amylases, cellulases, and
lipases, e) at least one biocidal quaternary ammonium compound
selected from the group consisting of di-n-decyl-dimethylammonium
chloride, didecyldimethylammonium bromide, dioctyldimethylammonium
chloride and mixtures thereof, and f) from 0.05 to 3 wt. % of
glutamic acid-N,N-diacetic acid.
2. A method for cleaning hard surfaces or textile fabrics using a
washing or cleaning agent according to claim 1, wherein the washing
or cleaning agent is brought into contact with the surface to be
cleaned or with the textile fabric.
3. The method according to claim 2, wherein the contact is carried
out by means of spray application.
Description
FIELD OF THE INVENTION
The present invention relates to a washing or cleaning agent having
an antimicrobial effect, which agent comprises at least one
tetracarboxylic acid or salts thereof in conjunction with at least
one biocidal quaternary ammonium compound.
BACKGROUND OF THE INVENTION
Microorganisms can be a substantial hygiene and health problem in
the household. The adherence of microorganisms to surfaces is
undesirable, in particular in the case of pathogenic
microorganisms. Adherent microorganisms often lead to infections or
to re-infections in humans, animals and even plants.
Delicate textiles such as silks or microfibers are being
increasingly made into clothing that can only be washed at 30 or
40.degree. C. Microorganisms are not safely killed off at such
temperatures. In addition to the lower washing temperatures, it is
also usual nowadays to use liquid washing agents that are generally
free of bleaching agents, which are antimicrobially active. In
addition, problems with unpleasant odors may also occur because
remaining germs reproduce on the laundry during drying, wearing or
storage and produce malodorous metabolic products.
However, the problem of the adhesion of microorganisms exists not
only on clothing or other textile fabrics, such as hand towels or
bed linen, but also when cleaning in the household itself, for
example hard surfaces such as floors, baths or even dishes.
The prevailing washing behavior means that textiles or surfaces
contaminated with viruses, bacteria or other microorganisms cannot
be sterilized to the required degree, causing infection or
re-infection in certain circumstances.
Antimicrobially active compounds and compositions as well as the
use thereof in washing agents are known in the prior art. For
example, WO 2013/064340 A1 discloses a cleaning agent for hard
surfaces having a pH in the range of from 9 to 12, which agent
comprises benzalkonium chloride, a salt of di- or tricarboxylic
acids, sodium tripolyphosphate and water.
WO 2012/055775 A1 describes quaternary ammonium compounds (QAC) as
microbially active compounds in liquid washing or cleaning agents.
However, it is precisely in such washing, cleaning or disinfecting
formulations which have biocidal quaternary ammonium compounds that
a concentration-dependent poor level of activity has been shown, in
particular in the case of gram-negative bacteria. Said bacteria
occur in particular in moist regions, as prevail in the bath or on
damp laundry.
BRIEF SUMMARY OF THE INVENTION
A problem addressed by the present invention is therefore that of
providing an antimicrobially active washing or cleaning agent
having at least one quaternary ammonium compound in which the
antimicrobial activity with respect to known formulations is
improved.
Surprisingly, it has been shown that an improved antimicrobial
effect of the quaternary ammonium compounds can be achieved by
means of tetracarboxylic acids or salts thereof, although
tetracarboxylic acids or salts thereof are not antimicrobially
active themselves. Surprisingly, a synergistic effect has been
found between the quaternary ammonium compounds and tetracarboxylic
acids or salts thereof.
By using a washing or cleaning agent according to the invention, a
hygiene effect can thus be achieved, even at low washing
temperatures and using liquid washing agents, that is comparable
with the hygiene performance of bleach-containing powdered washing
agents at high temperatures of 60.degree. C. or more. For cleaning
agents of hard surfaces, a prevailing poor level of activity
against pseudomonads or other microorganisms can be resolved in
this way.
The washing or cleaning agent according to the invention comprises
at least one tetracarboxylic acid or salts thereof
(tetracarbonates). In this case, the tetracarboxylic acid
preferably has one of the following general structures (Ia), (Ib)
or (Ic):
##STR00001##
The corresponding tetracarbonates correspondingly have the
following general structures (IIa), (IIb) or (IIc):
##STR00002##
If tetracarboxylic acids are described in the following,
tetracarbonates are correspondingly also to be understood thereby
and vice versa.
In the general structural formulas (Ia), (Ib) and (Ic) and (IIa),
(IIb) and (IIc), m, n, o and p, independently of one another, each
stand for natural integers in the range of from 0 to 10, in
particular 0 to 8, preferably 1 to 6, particularly 1 to 5 and
particularly preferably for 0, 1, 2, 3 or 4, and in particular for
0, 1 or 2.
The salt is preferably ammonium and/or alkali metal salt; Z.sup.+
preferably stands for NH.sub.4.sup.+, Na.sup.+ or K.sup.+.
A is preferably selected from a substituted or unsubstituted alkyl
or aryl functional group having 2 to 14 carbon atoms, or an element
of the 14th, 15th or 16th group of the periodic table (PTE). These
are naturally limited according to the valency of the atoms. It is
therefore obvious to a person skilled in the art that, in formula
(Ia) or (IIa), A does not stand for an element of the 15th or 16th
group of the PTE, and likewise in formula (Ib) or (IIb), elements
of the 16th group are excluded. Provided that as A has an open
valency, a hydrogen atom is bonded thereto.
"Alkyl" refers to a saturated aliphatic hydrocarbon, including
straight-chain and branched-chain groups. The alkyl group
preferably has 2 to 10 carbon atoms (when a numerical range such as
"2 to 10" is stated herein, this means that this group, in the
present case the alkyl group, may have 2 carbon atoms, 3 carbon
atoms, etc., up to and including 10 carbon atoms). In particular,
the alkyl may be a medium alkyl, having 2 to 6 carbon atoms, or a
lower alkyl, having 2 to 4 carbon atoms, for example ethyl,
n-propyl, isopropyl, butyl, isobutyl, tert-butyl, etc.
"Aryl" refers to monocyclic or polycyclic (i.e., rings having
shared neighboring carbon atom pairs) groups made up in particular
of 6 to 14 carbon ring atoms that have a complete conjugated pi
electron system. Examples of aryl groups are phenyl, naphthalenyl,
and anthracenyl.
The alkyl functional group and/or the aryl functional group may be
substituted. "Substituted," as used herein in conjunction with the
substituents and functional groups according to the invention,
means that, in the group in question, one or more H atoms and/or
one or more C atoms are replaced by other functional groups, these
functional groups being selected in particular from those
containing one or more heteroatoms. In various embodiments, the
substituents are selected from .dbd.O, .dbd.S, --OH, --SH,
--NH.sub.2, --NO.sub.2, --CN, --F, --Cl, --Br, C.sub.1-10 alkyl,
C.sub.2-10 alkenyl, C.sub.2-10 alkynyl, C.sub.3-8 cycloalkyl,
C.sub.6-14 aryl, a 5- to 10-membered heteroaryl ring in which 1 to
4 ring atoms are independently nitrogen, oxygen or sulfur, and a 5-
to 10-membered heteroalicyclic ring in which 1 to 3 ring atoms are
independently nitrogen, oxygen or sulfur.
Particularly preferably, the tetracarboxylic acid has the general
structural formula (Ib). Here, A preferably stands for an element
of the 15th group of the PTE. It is particularly preferably
nitrogen (N) or phosphorus (P). Particularly preferably, A stands
for N.
In this preferred embodiment, m, n, o and p, independently of one
another, each stand for 0, 1, 2, 3 or 4, in particular for 0, 1 or
2. Particularly preferably, the tetracarboxylic acid is glutamic
acid-N,N-diacetic acid, in which n=0, m and o=1 and p=2 and A
stands for N.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the antibacterial effect based on the concentration of
glutamic acid diacetic acid in a liquid washing agent with QAC;
and
FIG. 2 shows the antibacterial effect based on the concentration of
glutamic acid diacetic acid added to an all-purpose cleaner.
DETAILED DESCRIPTION OF THE INVENTION
The washing or cleaning agent preferably comprises at least 0.05
wt. % or more, based on the total weight of the washing or cleaning
agent, of the at least one tetracarboxylic acid or salts thereof.
It has been found that this proportion is necessary to allow the
QAC to have an enhancing effect. The washing or cleaning agent
preferably comprises the tetracarboxylic acids in a proportion of
from 0.05 wt. % to 5 wt. %, in particular 0.05 wt. % to 3 wt. %,
preferably 0.1 wt. % to 1 wt. %. Amounts higher than this do not
lead to additional enhancement of the antimicrobial effect of the
QAC, and therefore "more" does not lead to a substantial
improvement in performance.
Without being bound to this theory, it is assumed that the
tetracarboxylic acid, owing to the properties as a chelating agent,
allows access to the cell membrane of the microbes such that the
QAC have an improved attack effect. Surprisingly, it has been shown
that the tetracarboxylic acids are functional for both acidic and
neutral as well as alkaline pH values. The washing or cleaning
agent according to the invention can thus have a pH of 7, >7 or
<7.
The liquid washing or cleaning agent contains a biocidally active
quaternary ammonium compound as an essential component. Quaternary
ammonium compounds (QAC) that are suitable as biocidal active
ingredients have the general formula
(R.sup.1)(R.sup.2)(R.sup.3)(R.sup.4)N.sup.+X'', in which R.sup.1 to
R.sup.4 represent identical or different C.sub.1-C.sub.22 alkyl
functional groups, C.sub.7-C.sub.28 aralkyl functional groups or
heterocyclic functional groups, where two functional groups, or, in
the case of aromatic bonding such as in pyridine, even three
functional groups form, together with the nitrogen atom, the
heterocycle, for example a pyridinium or imidazolinium compound,
and X'' represents halide ions, sulfate ions, hydroxide ions, or
similar anions.
It is preferable for the biocidal quaternary ammonium compound to
be selected from the group comprising alkyltrimethylammonium
halides, dialkyldimethylammonium halides, benzalkonium salts,
pyridinium salts and mixtures thereof. It is particularly
preferable for the biocidal quaternary ammonium compound to be a
dialkyldimethylammonium halide selected from the group comprising
di-n-decyl-dimethylammonium chloride, didecyldimethylammonium
bromide, dioctyldimethylammonium chloride and mixtures thereof.
These biocidal quaternary ammonium compounds are effective against
viruses, bacteria, mold fungi or yeast fungi that adhere to
textiles.
QAC may be prepared by reacting tertiary amines with alkalizing
agents, for example methyl chloride, benzyl chloride, dimethyl
sulfate, dodecyl bromide, but also ethylene oxide. The alkylation
of tertiary amines with a long alkyl functional group and two
methyl groups is particularly simple; the quaternization of
tertiary amines with two long functional groups and a methyl group
may also be carried out under mild conditions using methyl
chloride. Amines having three long alkyl functional groups or
hydroxy-substituted alkyl functional groups are less reactive, and
are preferably quaternized with dimethyl sulfate, for example.
Suitable QAC are, for example, benzalkonium chloride
(N-alkyl-N,N-dimethyl-benzylammonium chloride, CAS No. 8001-54-5),
Benzalkon B (m,p-dichlorobenzyl-dimethyl-C12-alkylammonium
chloride, CAS No. 58390-78-6), benzoxonium chloride
(benzyl-dodecyl-bis-(2-hydroxyethyl)-ammonium-chloride),
cetrimonium bromide (N-hexadecyl-N,N,N-trimethylammonium bromide,
CAS No. 57-09-0), benzethonium chloride
(N,N-dimethyl-N-[2-[2-[p-(1,1,3,3-tetramethylbutyl)-phenoxy]ethoxy]ethyl]-
-benzylammonium chloride, CAS No. 121-54-0),
dialkyldimethylammonium chloride such as didecyldimethylammonium
chloride (CAS No. 7173-51-5), didecyldimethylammonium bromide (CAS
No. 2390-68-3), dioctyldimethylammonium chloride, 1-cetylpyridinium
chloride (CAS No. 123-03-5) and thiazolium iodides and mixtures
thereof.
Particularly preferred QAC are dialkyldimethylammonium chlorides,
in particular didecyldimethylammonium chloride,
N-octadecyl-N,N,N-trimethylammonium chloride,
N-hexadecyl-N,N,N-trimethylammonium chloride and the benzalkonium
chlorides having C8-C18-alkyl functional groups, in particular
C.sub.12-C.sub.14-alkylbenzyldimethylammonium chloride. Another
preferred biocidal compound is
methyl-N-(2-hydroxyethyl)-N,N-di(caproyloxyethyl)ammonium-methosulfate.
Aside from the fact that these biocidal compounds are effective
against numerous microorganisms, the cationic compounds attach
particularly well to cotton-containing fabrics and fabric
blends.
The dialkyldimethylammonium halides, the benzalkonium halides
and/or substituted benzalkonium halides are commercially available
as Bardac.RTM. or Barquat.RTM. ex Lonza, Marquat.RTM. ex Mason,
Variquat.RTM. ex Evonik Industries and Hyamine.RTM. ex Lonza, for
example.
The biocidal quaternary ammonium compound is preferably used in an
amount of from 0.1 wt. % to 20 wt. %, preferably 0.5 wt. % to 10
wt. %, and particularly preferably 1 wt. % to 5 wt. %, in each case
based on the total amount of the washing or cleaning agent. From a
toxicological and ecological perspective, it is particularly
preferable for the amount of biocidal quaternary ammonium compound
to be less than 3 wt. %.
The washing or cleaning agent according to the invention contains
at least one surfactant as another essential component. In this
case, the at least one surfactant can be a non-ionic, cationic,
anionic and/or zwitterionic surfactant. According to the invention,
soaps are not comprised by the surfactants, but may likewise be a
component of the washing or cleaning agent according to the
invention.
In this case, the washing or cleaning agent according to the
invention may comprise a surfactant or mixtures of 2, 3 or more
surfactants. If the washing or cleaning agent comprises more than
one surfactant, these can be 2, 3 or more different amphoteric
(zwitterionic) surfactants, for example. However, it is also
possible to combine 1, 2, 3 or more non-ionic surfactants, for
example having 1, 2, 3 or more cationic surfactants. Suitable
surfactants are sufficiently described in the prior art.
The washing or cleaning agent preferably comprises non-ionic and/or
cationic and/or zwitterionic surfactants. Preferred washing or
cleaning agents according to the invention are further
characterized in that they contain less than 1.0 wt. % and in
particular no anionic surfactant.
All non-ionic surfactants that are known to a person skilled in the
art can be used as non-ionic surfactants. Preferably, low-foaming
nonionic surfactants are used, in particular alkoxylated,
especially ethoxylated, low-foaming non-ionic surfactants.
Suitable non-ionic surfactants include alkyl glycosides of the
general formula RO(G).sub.x, for example, in which R corresponds to
a primary straight-chain or methyl-branched aliphatic functional
group, in particular an aliphatic functional group that is
methyl-branched in the 2 position, having 8 to 22, preferably 12 to
18 C atoms, and G is the symbol that stands for a glycose unit
having 5 or 6 C atoms, preferably for glucose. The degree of
oligomerization x, which indicates the distribution of
monoglycosides and oligoglycosides, is any number between 1 and 10;
preferably x is from 1.2 to 1.4.
Another class of preferred non-ionic surfactants, which are used
either as the sole non-ionic surfactant or in combination with
other non-ionic surfactants, are alkoxylated, preferably
ethoxylated or ethoxylated and propoxylated fatty acid alkyl
esters, preferably having 1 to 4 carbon atoms in the alkyl
chain.
The washing or cleaning agent according to the present invention
particularly preferably comprises one or more amine oxides as the
non-ionic surfactant. Amine oxides that can preferably be used are,
for example, N-coconut alkyl-N,N-dimethyl amine oxide, N-tallow
alkyl-N,N-dihydroxyethyl amine oxide, myristyl cetyl dimethyl amine
oxide or lauryldimethylamine oxide. The amount of amine oxide is
preferably up to 5 wt. %, more preferably between 0.5 and 3 wt. %
and particularly preferably between 1 and 2 wt. %, in each case
based on the total amount of liquid washing or cleaning agent.
One advantage of using an amine oxide is that, for liquid
formulations of washing or cleaning agents, the matrix thereof is
stabilized such that the presence of, for example, alkoxylated
fatty alcohols or even optical brighteners is stabilized.
In a preferred embodiment, the washing or cleaning agent according
to the invention further comprises one or more ethoxylated fatty
alcohols. Primary alcohols having preferably 8 to 18 C atoms and,
on average, 1 to 12 mols of ethylene oxide (EO) per mol of alcohol
are used in particular as alkoxylated fatty alcohols. However,
alcohol ethoxylates having linear functional groups of alcohols of
native origin having 12 to 18 C atoms, for example of coconut,
palm, tallow fatty or oleyl alcohol, and an average of 2 to 8 EO
per mol of alcohol are particularly preferred. Examples of
preferred ethoxylated alcohols are C.sub.12-14 alcohols having 3
EO, 4 EO or 7 EO, C.sub.12-18 alcohols having 3 EO, 5 EO or 7 EO,
and mixtures thereof. The degrees of ethoxylation indicated
represent statistical averages that can correspond to an integer or
a fractional number for a specific product. Preferred alcohol
ethoxylates have a narrowed homolog distribution (narrow range
ethoxylates, NRE). In addition to these non-ionic surfactants,
fatty alcohols having more than 12 EO can also be used. Examples of
these are tallow fatty alcohols having 14 EO, 25 EO, 30 EO, or 40
EO. Alkoxylated fatty alcohols that contain EO and PO groups
together in the molecule can also be used according to the
invention. Furthermore, a mixture of a (more highly) branched
ethoxylated fatty alcohol and an unbranched ethoxylated fatty
alcohol, such as a mixture of a C.sub.16-18 fatty alcohol having 7
EO and 2-propylheptanol having 7 EO. Particularly preferably, the
washing or cleaning agent contains a C.sub.12-18 fatty alcohol
having 7 EO as the alkoxylated fatty alcohol.
In an alternative embodiment, the liquid washing or cleaning agent
is free of alkoxylated fatty alcohols, since these lead to slight
clouding of the liquid washing or cleaning agent and, as a result,
to a product that is less aesthetically appealing for some
users.
In a preferred embodiment, the washing or cleaning agent contains,
based on the total amount of washing or cleaning agent, up to 2 wt.
% of optical brightener.
Suitable optical brighteners comprise, for example, compounds from
the classes of bisstyrylbenzenes, Silibene, benzoxazoles,
coumarins, pyrenes and naphthalenes. Commercially available optical
brighteners are sold under the trademarks Tinopal.RTM., Uvitex.RTM.
(both from Ciba Speciality Chemicals), Ultraphor.RTM. (BASF SE) and
Blankophor.RTM. (Bayer).
Particularly preferred optical brighteners include
disodium-4,4'-bis-(2-morpholino-4-anilino-striazine-6-yl
amino)stilbene disulfonate,
disodium-2,2'-bis-(phenyl-styryl)disulfonate,
4,4'-bis[(4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazine-2-yl)amin-
o]stilbene-2,2'-disulfonic acid,
hexasodium-2,2'-[vinylenebis[(3-sulphonato-4,1-phenylene)imino[6-(diethyl-
amino)-1,3,5-triazine-4,2-diyl]imino]]bis-(benzene-1,4-disulfonate),
2,2'-(2,5-thiophendiyl)bis[5-1,1-dimethylethyl)-benzoxazole,
4-methyl-7-(diethylamino)coumarin and/or
2,5-bis(benzoxazole-2-yl)thiophene.
In a preferred embodiment, the washing or cleaning agent is a solid
cleaning agent. In a likewise preferred embodiment, the washing or
cleaning agent is liquid. In the case of a liquid washing or
cleaning agent, another preferred ingredient is boric acid or a
salt of the boric acid. If the liquid washing or cleaning agent
contains a salt of boric acid, it is particularly preferred for
this to be potassium salt, i.e. potassium borate. The addition of
boric acid or a salt of boric acid (borate) leads to an increase in
the antimicrobial performance of the liquid washing or cleaning
agent. In particular, the antimicrobial performance against fungi
is increased, it being possible to observe a particular increase in
performance against Candida albicans.
Using the washing or cleaning agent according to the invention, an
excellent antimicrobial performance is also achieved in the absence
of conventional disinfectants such as bleaching agents, for example
halogens, halogenated compounds or bleaching agents based on active
oxygen. However, it is also possible for the washing or cleaning
agent according to the invention to comprise, in addition to the
QAC, one of the mentioned conventional antimicrobial agents.
However, the washing or cleaning agent according to the invention
is preferably free of these.
In a preferred embodiment, the washing or cleaning agent according
to the invention further comprises a water-soluble salt, in
particular in the case of liquid washing or cleaning agents. The
salt influences the viscosity of the composition. In this case, the
salt can either be inorganic or organic. The washing or cleaning
agent in liquid form preferably comprises an inorganic salt, which
is preferably selected from the group that comprises colorless,
water-soluble halides, sulfites, carbonates, hydrogen carbonates,
nitrates, nitrites, phosphates and/or alkali metal oxides,
alkaline-earth metal oxides, aluminum oxides and/or transition
metal oxides. In addition, ammonium salts can also be used.
Particularly preferred are halides and sulfates of alkali metals,
particularly preferred are sodium chloride, potassium chloride,
sodium sulfate, potassium sulfate and mixtures of these salts.
Sodium chloride is particularly preferred.
If an organic salt is used, colorless water-soluble salts of a
carboxylic acid are particularly preferred. In this case, the salt
may be an alkali metal salt, alkaline-earth metal salt, ammonium
salt, aluminum salt, and/or transition metal salt. The salt is
preferably selected from the group comprising formiates, acetates,
propionates, citrates, maleates, tartrates, succinates, malonates,
oxalates, lactates and mixtures thereof.
In addition to the three essential components, the washing or
cleaning agent can contain further ingredients which further
improve the practical and/or aesthetic properties of the washing or
cleaning agent. Within the scope of the present invention, the
washing or cleaning agent additionally contains one or more
substances from the group of non-ionic surfactants, builders,
bleaching agents, bleach catalysts, bleach activators, enzymes,
electrolytes, non-aqueous solvents, pH adjusters, perfume
compositions, perfume carriers, fluorescing agents, dyes,
hydrotropic substances, foam inhibitors, silicone oils, soil
release polymers, graying inhibitors, anti-shrink agents, crease
protection agents, dye transfer inhibitors, additional
antimicrobial active ingredients, germicides, fungicides,
antioxidants, preservatives, corrosion inhibitors, antistatic
agents, bitters, ironing aids, repellents and impregnating agents,
swelling agents and non-slip agents, softening components and UV
absorbers.
The use of builder substances (builders) such as silicates,
aluminum silicates (particularly zeolites), salts of organic di-
and polycarboxylic acids, as well as mixtures of these substances,
preferably water-soluble builder substances, in the washing or
cleaning agent according to the invention can be advantageous. The
builders include, in particular, carbonates, citrates,
phosphonates, organic builders, and silicates. The proportion by
weight of the total builders with respect to the total weight of
washing or cleaning agents according to the invention is preferably
15 to 80 wt. % and in particular 20 to 70 wt. %.
In an embodiment that is preferred according to the invention, the
use of phosphates (including polyphosphates) is omitted either
largely or completely. In this embodiment, the washing or cleaning
agent preferably contains less than 5 wt. %, particularly
preferably less than 3 wt. %, in particular less than 1 wt. %
phosphate(s). Particularly preferably, the washing or cleaning
agent in this embodiment is completely phosphate-free, i.e., the
washing or cleaning agents contain less than 0.1 wt. %
phosphate(s).
In another embodiment, the present invention relates to the use of
tetracarboxylic acids and salts thereof for synergistically
enhancing the antimicrobial effect of biocidal quaternary ammonium
compounds in washing or cleaning agents. With regard to preferred
embodiments, reference is made to the above embodiments. The
tetracarboxylic acid glutamic acid-N,N-diacetic acid is preferred.
The salt of the tetracarboxylic acid is preferably ammonium salt or
an alkali metal salt.
The invention also relates to the use of a washing or cleaning
agent according to the invention in washing, cleaning and/or
pretreating textile fabrics or hard surfaces. Washing or cleaning
agents within the meaning of the present invention are in
particular household cleaners, washing, cleaning or pretreatment
agents or freshening sprays for textiles, fabric softeners,
cosmetic products or air care products, for example room sprays or
air fresheners. Household cleaners within the meaning of the
present invention are, for example, cleaning agents for cleaning
hard surfaces, window cleaners, bath cleaners, WC cleaners or
dishwashing detergents (hand dishwashing detergents and dishwashing
detergents for machine use). Cosmetic products within the meaning
of the present invention are products for the cosmetic treatment of
skin and hair (skin treatment agents, hair treatment agents), for
example hair shampoos, hair rinses, deep conditioners,
conditioners, agents for bleaching, coloring or shaping the hair,
such as coloring agents, bleaching agents, toning agent,
color-fixing agents, wave-setting agents or styling preparations
such as hair stabilizers, styling mousses or styling gels, shower
gels, body creams, body lotions, face creams or deodorants.
In a preferred embodiment of the invention, the washing or cleaning
agent is a washing or cleaning agent in liquid form, preferably in
gel form. Preferred liquid washing or cleaning agents have a water
content of in particular from 3 to 95 wt. %, preferably 8 to 80 wt.
%, and in particular 25 to 70 wt. %, based on the total weight of
the washing or cleaning agent. In the case of liquid concentrates,
the water content may also be lower and may be 30 wt. % or less,
preferably 20 wt. % or less, in particular 15 wt. % or less. Here
too, the specifications in wt. % are in each case based on the
total weight of the agent. In addition to water, the liquid agents
can also have additional non-aqueous solvents. A preferred liquid,
in particular gel-form, washing agent according to the invention
can preferably comprise components selected from the following:
anionic surfactants, such as preferably alkylbenzene sulfonate,
alkyl sulfate, in particular in a proportion of from 5 to 40 wt. %;
in this case one anionic surfactant or mixtures of different
anionic surfactants may be contained, non-ionic surfactants, such
as preferably fatty alcohol polyglycol ether, alkyl polyglucoside,
fatty acid glucamide, preferably in amounts of from 0.5 to 25 wt. %
of one or more non-ionic surfactants, one or more builders, for
example zeolite, polycarboxylate, sodium citrate, advantageously in
an amount of from 0 to 15 wt. %, preferably 0.01 to 10 wt. %, in
particular 0.1 to 5 wt. %, one or more foam inhibitors, for example
soap, silicone oils, paraffins, preferably in amounts of from 0 to
10 wt. %, advantageously 0.1 to 4 wt. %, preferably 0.2 to 2 wt. %,
in particular 1 to 3 wt. %, enzymes, for example proteases,
amylases, cellulases, lipases, preferably in amounts of from 0 to 3
wt. %, advantageously 0.1 to 2 wt. %, preferably 0.2 to 1 wt. %, in
particular 0.3 to 0.8 wt. %, optical brighteners, for example
stilbene derivative, biphenyl derivative, in particular in amounts
of from 0 to 1 wt. %, advantageously 0.1 to 0.3 wt. %, in
particular 0.1 to 0.4 wt. %, optionally fragrances, for example
perfume oils, optionally stabilizers, water, optionally soap, in
particular from 0 to 25 wt. %, advantageously 1 to 20 wt. %,
preferably 2 to 15 wt. %, particularly 5 to 10 wt. %, optionally
non-aqueous solvent, in particular alcohols, advantageously from 0
to 25 wt. %, preferably 1 to 20 wt. %, in particular 2 to 15 wt. %.
The specifications in wt. % refer in each case to the total weight
of the washing or cleaning agent.
In another preferred embodiment, the washing or cleaning agent is a
liquid softener, which can preferably contain additional components
that are selected from the following: cationic surfactants, such as
in particular esterquats, preferably in amounts of from 5 to 30 wt.
%, cosurfactants, for example glycerol monostearate, stearic acid,
fatty alcohols, fatty alcohol ethoxylates, in particular in amounts
of from 0 to 5 wt. %, preferably 0.1 to 4 wt. %, emulsifiers, for
example fatty amine ethoxylates, in particular in amounts of from 0
to 4 wt. %, preferably 0.1 to 3 wt. %, optionally fragrances, for
example perfume oils, optionally dyes, preferably in the ppm range,
optionally stabilizers, preferably in the ppm range, Solvents, such
as in particular water, in amounts of preferably 60 to 90 wt. %.
The specifications in wt. % relate in each case to the total weight
of the formulation, i.e. of the softener. The specifications in ppm
refer to the weight (wt. ppm).
A washing or cleaning agent according to the invention is prepared
by means of conventional and known methods and processes.
The present invention further relates to a method for cleaning hard
surfaces or textile fabrics using tetracarboxylic acids or salts
thereof or a washing or cleaning agent as described above, in which
method the tetracarboxylic acid and salts thereof or the washing or
cleaning agent according to the invention are brought into contact
with the surface to be cleaned/with the textile fabric. The contact
can be carried out, for example, by the washing or cleaning agent
or the tetracarboxylic acid or tetracarbonate being applied to the
surface to be cleaned/to the textile fabric to be cleaned by means
of spray application. Hard surfaces in particular can also be
cleaned by bringing a cleaning cloth, which comprises a washing or
cleaning agent according to the invention or tetracarboxylic
acid/tetracarbonate together with biocidal quaternary ammonium
compounds, into contact with the hard surface. It is also possible
for a corresponding cleaning cloth, for example when
machine-cleaning textile fabrics, to be added into a washing
machine together with said fabrics, so as to allow an enhanced
antimicrobial effect during the washing cycle.
EMBODIMENTS
Example 1: QAC-Containing Washing Agent for Textiles
A commercially available liquid washing agent, which comprised 2.2%
a.i. QAC (benzalkonium chloride), was used as a reference. The pH
was approximately 6. The washing agent had the following
composition:
TABLE-US-00001 Components: Proportion in % a.i. Anionic surfactant
1-10 Non-ionic surfactant 2-8 Builder (citric acid and
phosphonates) 0-3 Caustic soda 0.1-1.sup. Palm kernel oil fatty
acid 0-1 Glycerol 0-1 Sodium chloride 0.5-3.sup. Enzymes (protease,
amylase, cellulase, 0-3 lipase) Boric acid 0.1-2.sup. Other
additives (preservative, defoamer, 0-1 optical brightener, dye,
perfume) Water Remainder a.i.: active ingredient
The washing agent was used in a test for determining the reduction
of Pseudomonas aeruginosa according to EN 1276. The obtained value
served as a reference.
0.10 wt. % GLDA or 0.50 wt. % were then added to the washing agent
and likewise used in the test for determining the reduction of
Pseudomonas aeruginosa according to EN 1276.
In the following Table 1, the proportions of QAC and GLDA are again
summarized.
TABLE-US-00002 TABLE 1 Glutamic acid Concentration glutamic
diacetic acid Liquid washing acid diacetic acid (GLDA) agent with
QAC 0.00% (reference) 4.60E+01 0.10% (according to the invention)
7.65E+00 8.70E+03 0.50% (according to the invention) 6.90E+01
1.90E+05
The results of the measurement are shown in FIG. 1.
Using the liquid washing agent, which exclusively comprised QAC,
the number of pathogens could be reduced. An antibacterial effect
can be observed here owing to the QAC. Surprisingly, the effect
could be significantly enhanced by using GLDA, although GLDA itself
does not have an antimicrobial effect.
Example 2: QAC-Containing All-Purpose Cleaner
A commercially available liquid all-purpose cleaner, which
comprised 0.5% a.i. QAC (DDAC), was used as a reference. The pH was
approximately 5. The cleaner had the following composition:
TABLE-US-00003 Components: Wt. % Na citrate 15.00-20.00 Na
Percarbonate 10.00-15.00 QAC 0.1-3.sup. Amphoteric surfactant
0.00-10.00 Non-ionic surfactant 0.00-10.00 Builder 0.00-10.00
Cationic copolymer 0.00-0.75 Enzymes 2.00-8.00 Other additives
(preservative, defoamer, optical brightener, 0.05-10.00 dye,
perfume, etc.) Water Remainder (ad 100)
The all-purpose cleaner was used in a test for determining the
reduction of Pseudomonas aeruginosa according to EN 1276. The
obtained value served as a reference.
0.10 wt. % GLDA or 0.50 wt. % were then added to the all-purpose
cleaner and likewise used in the test for determining the reduction
of Pseudomonas aeruginosa according to EN 1276.
In the following Table 2, the proportions of QAC and GLDA are again
summarized.
TABLE-US-00004 TABLE 2 Concentration glutamic Glutamic acid
All-purpose acid diacetic acid diacetic acid (5%) cleaner 0.00%
(reference) 1.9E+02 0.10% (according to the invention) 7.65E+00
3.1E+05 0.50% (according to the invention) 6.90E+01 3.1E+05
The results are shown in FIG. 2.
Using the all-purpose cleaner, which exclusively comprised QAC, the
number of pathogens could be reduced. An antibacterial effect can
be observed here owing to the QAC. Surprisingly, the effect could
be significantly enhanced by using GLDA, although GLDA itself does
not have an antimicrobial effect.
* * * * *